CN106164167A - Polyacetal resin composite and molded body thereof - Google Patents

Abstract

It is an object of the invention to provide a kind of resin combination, described resin combination can manufacture the molded body with high-durability, sliding and wearability in high production rate ground.The present invention provides a kind of polyacetal resin composite, described polyacetal resin composite comprises (B) category of glass packing material of below more than (A) polyacetal resin of 100 mass parts and 10 mass parts and 100 mass parts, when the molded body this polyacetal resin composite molding obtained is carried out tension failure, the composition comprising (A) polyacetal resin being averaged below more than thickness 0.2 μm and 3.0 μm from the surface of prominent (B) the category of glass packing material of the plane of disruption of post-rift molded body covers.

Description

Polyacetal resin composite and molded body thereof

Technical field

The present invention relates to polyacetal resin composite and molded body thereof.

Background technology

The polyacetal resin such as mechanical strength such as the modulus of elasticity in static bending and tensile break stress, chemical-resistant, sliding And the balancing good of wearability, and it is easily worked.Therefore, polyacetal resin as typical engineering plastics at electrical equipment Mechanism part and the scope widely such as automotive part in use.

Especially, the automotive part require durability uses the polyacetal resin after utilizing inorganic filler strengthening Compositions.The rupture life that durability refers to such as under certain stress is long, also referred to as creep resistant.

For the polyacetal resin composite after the strengthening comprising inorganic filler, in order to improve durability, carry out The macromolecule of polyacetal resin quantifies, the control of the end group of polyacetal resin.

Patent Document 1 discloses and comprise polyacetal resin and threadiness is inorganic fills out for improving the purpose of creep resistant Fill the polyacetal resin composite of material.It addition, the molecular weight the most resistance to the biggest creep that Patent Document 1 discloses polyacetal resin Property more improve.

Patent Document 2 discloses following method, at the bunching comprising category of glass inorganic filling material and polyacetal resin In urea formaldehyde compositions, in order to improve the adhesiveness at the interface of category of glass inorganic filling material and polyacetal resin and and use end The multiple polyacetal resin that the content of hydroxyl is different.

Patent Document 3 discloses the ABA block polymer comprising polyacetals skeleton by use to improve and glass The adhesiveness of fiber etc..

It addition, the expansion of the application corresponding to polyacetal resin, it is desirable to the improvement of wearability.Have studied by tree Oil/fat composition adds ultra-high molecular weight polyethylene and improves wearability.

Patent Document 4 discloses and coordinate to improve the wearability of the polyacetal resin composite comprising glass fibre Lubricant.It addition, Patent Document 4 discloses preferred ultra-high molecular weight polyethylene as lubricant.

Patent Document 5 discloses and comprising glass fibers for the purpose improving mechanical strength, wearability and sliding Friction fit modifying agent in the polyacetal resin composite of dimension.Particularly disclosing friction modifiers, to be preferably mean molecule quantity big In 1.0 × 10⁶The ultra-high molecular weight polyethylene of g/ mole.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 11-181231 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2004-359791 publication

Patent documentation 3: International Publication the 2001/009213rd

Patent documentation 4: Japanese Unexamined Patent Publication 9-272802 publication

Patent documentation 5: Japanese Unexamined Patent Application Publication 2014-534301 publication

Summary of the invention

Invent problem to be solved

In recent years, for using the mechanism part of polyacetal resin, automotive part etc., it is desirable to further high property Energyization and high-quality.

As high performance, specifically, the raising of mechanical strength, durability and wearability can be enumerated.As high-quality Change, specifically, suppression bad order can be enumerated.

But, when making polyacetal resin macromolecule quantify to improve durability, mobility declines and is difficult to molding, because of This causes the qualities such as bad order to decline.

During it addition, the terminal hydroxyl of polyacetal resin increases, heat stability declines, and therefore causes bad order during molding Qualities such as (crazings) declines.

Additionally, in the case of adding ultra-high molecular weight polyethylene to improve wearability, owing to super high molecular weight is gathered The coming off etc. and easily produce chip of ethylene.Further, since the increase of chip, the charging being susceptible in forming machine bad and Molding cycle increases, it is also possible to cause the decline of productivity ratio.

Conventional polyacetal resin composite disclosed in patent documentation 1～5 can not manufacture excellent in te pins of durability, have High wearability and mechanical strength and the also excellent molded body of outward appearance.

The problem that the invention solves the problems that is to provide a kind of resin combination, and described resin combination can high production rate ground Manufacture the molded body with high durability, sliding and wearability.

Means for solving the above

The present inventor conducts in-depth research to solve above-mentioned problem.Result is it has surprisingly been found that pass through to be formed The category of glass packing material comprising ormal weight and the polyacetal resin composite of the molded body that may be made with particular characteristics, permissible Solve above-mentioned problem, thus complete the present invention.

That is, the present invention is as described below.

[1] a kind of polyacetal resin composite, described polyacetal resin composite comprises (A) polyacetals of 100 mass parts (B) category of glass packing material more than resin and 10 mass parts and below 100 mass parts, wherein,

When the molded body this polyacetal resin composite molding obtained is carried out tension failure, from post-rift one-tenth The surface of (B) category of glass packing material that the plane of disruption of type body is prominent is averaged comprising of below more than thickness 0.2 μm and 3.0 μm (A) composition of polyacetal resin covers.

[2] a kind of polyacetal resin composite, described polyacetal resin composite comprises (A) polyacetals of 100 mass parts (B) category of glass packing material more than resin and 10 mass parts and below 100 mass parts, wherein,

The tensile break stress according to ISO527-1 of the molded body this polyacetal resin composite molding obtained is More than 135MPa,

The modulus of elasticity in static bending according to ISO 178 of this molded body is more than 7500MPa, and

(tensile break stress-65) (MPa)/category of glass packing material ratio (quality %) is more than 2.90.

[3] polyacetal resin composite as described in [2], wherein, to by described polyacetal resin composite molding When the molded body obtained carries out tension failure, from prominent (B) the category of glass packing material of the plane of disruption of post-rift molded body Surface is averaged the composition comprising (A) polyacetal resin of below more than thickness 0.2 μm and 3.0 μm and covers.

[4] polyacetal resin composite as according to any one of [1]～[3], wherein, relative to described (A) polyacetals Resin 100 mass parts, described polyacetal resin composite also comprises (C) weight average of below more than 0.5 mass parts and 8 mass parts and divides Son amount is the polyvinyl resin of less than 500,000.

[5] polyacetal resin composite as described in [4], wherein, described (C) weight average molecular weight is the poly-second of less than 500,000 The fusing point of olefine resin is less than 115 DEG C.

[6] polyacetal resin composite as according to any one of [1]～[5], wherein, described polyacetal resin composite Comprise at least one sour modifying surface as the category of glass packing material having described (B) category of glass packing material The material of function.

[7] polyacetal resin composite as described in [6], wherein, described acid is carboxylic acid.

[8] polyacetal resin composite as according to any one of [1]～[7], wherein, described (A) polyacetal resin bag Containing block component.

[9] polyacetal resin composite as described in [8], wherein, described block component is hydrogenated butadiene polymer composition.

[10] a kind of molded body, it is by obtaining the polyacetal resin composite molding according to any one of [1]～[9] Arrive.

[11] molded body as described in [10], wherein, described molded body comprise (C) weight average molecular weight be less than 500,000 poly- Vinyl, the amount of the polyvinyl resin that (C) weight average molecular weight is less than 500,000 in the top layer of molded body is more than will be away from The degree of depth on the top layer of molded body is less than 500,000 more than (C) weight average molecular weight in the top layer in the face after the layer cutting of 1,000 μm The amount of polyvinyl resin.

[12] manufacture method of a kind of polyacetal resin composite according to any one of [1]～[9], comprising:

Utilization comprises at least one acid and has the material of function of modifying surface to (B) category of glass packing material Operation to the modifying surface of (B) category of glass packing material；With

The operation that category of glass packing material and (A) polyacetal resin through described modification is mixed.

Invention effect

According to the present invention it is possible to provide a kind of resin combination, described resin combination can manufacture tool in high production rate ground There is the molded body of high durability, sliding and wearability.

Accompanying drawing explanation

Fig. 1 represents the relation of tensile break stress (MPa) and category of glass packing material ratio (quality %).

Detailed description of the invention

Hereinafter, the mode (hereinafter referred to as embodiment) for implementing the present invention is described in detail.Following reality The mode of executing is the illustration for the present invention is described, the present invention is not limited to content below.The present invention can be in its purport In the range of carry out implementing after various deformation.

[polyacetal resin composite]

The polyacetal resin composite of present embodiment is to comprise 100 mass parts (A) polyacetal resin and 10 mass parts The polyacetal resin composite of (B) the category of glass packing material above and below 100 mass parts, to comprising this polyacetal resin When the molded body of compositions carries out tension failure, from (B) category of glass packing material that the plane of disruption of post-rift molded body is prominent Surface be averaged below more than thickness 0.2 μm and 3.0 μm the composition comprising (A) polyacetal resin cover.

The content of (B) the category of glass packing material in present embodiment is 10 relative to (A) polyacetal resin 100 mass parts More than mass parts and below 100 mass parts.

Being more than 10 mass parts by this content, mechanical strength, creep resistant improve.

It addition, be below 100 mass parts by this content, it is possible to when molding, suppression is because of category of glass packing material each other The fracture of the category of glass packing material contacted and cause.Therefore, mechanical strength, creep resistant improve.Additionally, by this content be Below 100 mass parts, it is possible to carry out stable extrusion molding, it is possible to the bad order of suppression molded body.

The lower limit of this content is preferably 12 mass parts, more preferably 15 mass parts, more preferably 20 mass parts, more More preferably 25 mass parts.

The higher limit of this content is preferably 90 mass parts, more preferably 80 mass parts, more preferably 75 mass parts, more More preferably 70 mass parts.

In the present embodiment, when the molded body comprising polyacetal resin composite is carried out tension failure, cover from The one-tenth comprising polyacetal resin composite on the surface of (B) category of glass packing material that the plane of disruption of post-rift molded body is prominent The average thickness divided is below more than 0.2 μm and 3.0 μm.

Being more than 0.2 μm by this average thickness, creep resistant, mechanical strength improve.It addition, can suppress chip and The bad order of the molded body obtained by suppression, therefore quality improves.Additionally, due to molding cycle shortens and productivity ratio raising.

It addition, be below 3.0 μm by this average thickness, it is possible under the mobility of suppression polyacetal resin composite Fall, thus suppress the bad order of molded body.

The lower limit of this average thickness is preferably 0.3 μm, more preferably 0.4 μm.

The higher limit of this average thickness is preferably 2.5 μm, more preferably 2.0 μm.

In the present embodiment, foundation ISO 294-polyacetal resin composite being carried out injection moulding and obtain is used The molded body of the compact tensile test film shape of 1, is shaped the tension failure of body for 50mm/ minute with draw speed.

In the present embodiment, the molded body with arbitrary shape is being measured the table covering (B) category of glass packing material During the average thickness of the composition comprising polyacetal resin composite in face, it is possible to use the molded body with arbitrary shape is passed through Hot pressing and be reprocessed into the molded body of compact tensile test film shape and carry out.

Hot pressing when being reprocessed into compact tensile test film shape is entered within 5 minutes by the temperature below 220 DEG C OK, can obtain the molded body that is reprocessed into and not to cover (B) category of glass packing material surface comprise polyacetal resin The average thickness of the composition of compositions impacts.

Compact tensile can not be reprocessed into by hot pressing try owing to having the size of the molded body of arbitrary shape, shape etc. When testing plate shape, the molded body with arbitrary shape can be directly used to carry out tension failure.

In the present embodiment, (B) category of glass filling material that the plane of disruption of the molded body after tension failure is prominent is covered The average thickness of the composition comprising polyacetal resin composite on the surface of material can be by utilizing scanning electron microscope (SEM) The plane of disruption of the molded body after tension failure is observed and obtains.

Although being not particularly limited, as (B) category of glass packing material, as a example by glass fibre, average below for this The assay method of thickness is specifically described.

In the present embodiment, the composition comprising polyacetal resin composite on the surface to cover glass fiber is flat When all thickness is measured, as glass fibre to be measured, preferably select the plane of disruption of the molded body after tension failure The glass fibre existed near central authorities.

First, at least 50 glass fibre highlighted from the plane of disruption it are randomly chosen.Then, to covering this glass fibre The layer on surface is observed, and measures the thickness of layer.During layer in uneven thickness, use maximum as the thickness of this layer.So After, the thickness of 50 layers is carried out addition and is averaging, thus calculate average thickness.

In the case of the surface of resinous principle cover glass fiber equably, glass fibre and the layer covering surface sometimes Between boundary unintelligible.In this case, the single diameter of glass fibre can be used when calculated thickness.Such as exist In the case of resinous principle covers the surface that cross section is circular glass fibre equably, under the thickness of the layer covering surface passes through Formula is obtained.

Cover thickness=(comprising the single diameter of diameter-glass fibre of layer)/2 of the layer on surface

The single diameter of glass fibre can be asked by measuring the residue after removing resinous principle from molded body Go out.

As the method removing resinous principle from molded body, can enumerate such as: right in the highest temperature (more than 400 DEG C) The method that resinous principle in molded body carries out burning；Impregnated in the solvent of dissolving (A) polyacetal resin and by molded body The method that resinous principle removes；Deng.

In the present embodiment, preferably: the surface of (B) category of glass packing material in terms of area ratio preferably more than 50%, More preferably more than 70%, further preferred more than 80%, the most preferably more than 90% one-tenth being comprised (A) polyacetal resin Divide and cover.

Being more than 50% by area ratio, the creep resistant of molded body improves further.

In order to make what the surface of (B) category of glass packing material was averaged below more than thickness 0.2 μm and 3.0 μm to comprise bunching The composition of urea formaldehyde compositions covers, and can enumerate such as: use block copolymer described later as (A) polyacetal resin；And Use described later comprise acid material as the function of the modifying surface having (B) category of glass filler material (with Under be sometimes designated as film former)；Deng.

Wherein, and with block copolymer and comprise acid film former time, (A) polyacetal resin and (B) category of glass fill material The adhesivity at interface of material significantly improves, cover (B) category of glass packing material surface comprise polyacetal resin composite The average thickness of composition increases.

In order to make this average thickness within the above range, when manufacturing polyacetal resin composite by melting mixing, will (B) category of glass packing material and (A) polyacetal resin carry out the mixing of longer time is also effective.Generally, it is considered that at resin During the melting mixing of compositions, preferably category of glass packing material carries out mixing with shorter time, but shape in the present embodiment Become contrary trend.Specifically can enumerate: in the case of being supplied (B) category of glass packing material when extruding mixing by side charger, (B) category of glass packing material is supplied from more upstream side.

In the present embodiment, constitute cover (B) category of glass packing material surface layer comprise polyacetal resin group The composition of compound can be (A) polyacetal resin be main component and to comprise (C) described later weight average molecular weight be less than 500,000 The resinous principle of polyvinyl resin and/or stabilizer etc..

The polyacetal resin composite of present embodiment comprise (A) polyacetal resin of 100 mass parts and 10 mass parts with (B) category of glass packing material above and below 100 mass parts, the molded body that this polyacetal resin composite molding is obtained Tensile break stress according to ISO527-1 is more than 135MPa, and the modulus of elasticity in static bending according to ISO 178 of this molded body is More than 7500MPa, and the value of (tensile break stress-65) (MPa)/category of glass packing material ratio (quality %) be 2.90 with On.

The content of (B) the category of glass packing material in present embodiment is 10 relative to (A) polyacetal resin 100 mass parts More than mass parts and below 100 mass parts.

Being more than 10 mass parts by this content, mechanical strength, creep resistant improve.

It addition, be below 100 mass parts by this content, can suppress when molding because of category of glass packing material each other The fracture of the category of glass packing material contacted and cause.Therefore, mechanical strength, creep resistant improve.Additionally, due to mobility carries High, it is thus possible to carry out stable extrusion molding, it is possible to the bad order of suppression molded body.

The lower limit of this content is preferably 12 mass parts, more preferably 15 mass parts, more preferably 20 mass parts, more More preferably 25 mass parts.

The higher limit of this content is preferably 90 mass parts, more preferably 80 mass parts, more preferably 75 mass parts, more More preferably 70 mass parts.

In the present embodiment, the drawing according to ISO527-1 of molded body polyacetal resin composite molding obtained Stretching fracture strength is more than 135MPa.

This tensile break stress is preferably more than 140MPa, more preferably more than 145MPa, more preferably 150MPa Above, the most preferably more than 155MPa.

In the present embodiment, the foundation ISO's 178 of molded body polyacetal resin composite molding obtained is curved Modulus in elasticity in bending is more than 7500MPa.

This modulus of elasticity in static bending is preferably more than 8000MPa, more preferably more than 8500MPa, more preferably More than 9000MPa, the most preferably more than 9500MPa.

By tensile break stress be more than 135MPa, the modulus of elasticity in static bending be more than 7500MPa, it is possible to mechanical strength Requirement higher purposes extension.

It addition, be more than 7500MPa by the modulus of elasticity in static bending, it is possible to realize the thin-walled property of molded body, it is possible to achievement unit The miniaturization of part, lightweight.

In the present embodiment, the tensile break stress of molded body and the mensuration of the modulus of elasticity in static bending use polyacetals tree Oil/fat composition injection moulding and the molded body of compact tensile test film shape according to ISO 294-1 that obtains is carried out.

In the present embodiment, the molded body with arbitrary shape is obtained tensile break stress and the modulus of elasticity in static bending Time, it is possible to use by hot pressing, the molded body with arbitrary shape is reprocessed into the molded body of compact tensile test film shape Carry out.

Hot pressing when being reprocessed into compact tensile test film shape is entered within 5 minutes by the temperature below 220 DEG C OK, the molded body being reprocessed into can be obtained.

Compact tensile can not be reprocessed into by hot pressing try owing to having the size of the molded body of arbitrary shape, shape etc. When testing plate shape, the molded body with arbitrary shape can be directly used to carry out the survey of tensile break stress and the modulus of elasticity in static bending Fixed.

The tensile break stress of molded body carries out tension test according to ISO 527-1 for 5mm/ minute with draw speed and surveys Fixed.

Measure it addition, the modulus of elasticity in static bending of molded body is curved test according to ISO 178.

In the present embodiment, (tensile break stress-65) (MPa)/category of glass packing material ratio (quality %) is More than 2.90, preferably more than 2.95, more preferably more than 3.00, more preferably more than 3.05.

The higher limit of (tensile break stress-65) (MPa)/category of glass packing material ratio (quality %) limits the most especially Fixed, preferably less than 4.00, more preferably less than 3.75.

The value of (tensile break stress-65) (MPa)/category of glass packing material ratio (quality %) represents at polyacetal resin The contribution that tensile break stress is improved by the per unit compounding ratio of (B) the category of glass packing material coordinated in compositions.

(tensile break stress-65 (MPa))/category of glass packing material ratio (quality %) is more than 2.90 to refer to, such as Fig. 1 Shown in, with category of glass packing material ratio as transverse axis, with tensile break stress for the longitudinal axis draw time, for present embodiment Polyacetal resin composite for, the relation of category of glass packing material ratio and tensile break stress is in intercept 65MPa, tiltedly Rate be 2.90 straight line (1) is upper or the top of straight line (1).

In formula, 65MPa is that the tension failure of (A) polyacetal resin of the state of unmated (B) category of glass packing material should The value of power.In the present embodiment, even if the molecular weight of (A) polyacetal resin, structure etc. change, this value of 65MPa is made The value of tensile break stress for (A) polyacetal resin of the state of unmated (B) category of glass packing material becomes hardly Change.

In the past, for comprising the molded body of the polyacetal resin of category of glass packing material, fill out by improving category of glass Filling the use level of material, the modulus of elasticity in static bending improves.On the other hand, it is greater than about 30 mass % with category of glass packing material ratio When amount coordinates category of glass packing material, tensile break stress has the trend (curve (3) in Fig. 1) almost no longer improved.Cause This, it is difficult to obtain the molded body that tensile break stress is more than 135MPa.Its reason is the most uncertain, it is believed that be because polyacetals tree Fat is low with the adhesivity of category of glass packing material, and under tensile stress, their interface becomes the starting point of fracture.

The molded body of the conventional polyacetal resin that tensile break stress is relatively low relative to the modulus of elasticity in static bending exists durable Property not enough problem.It addition, when the melting mixing of polyacetal resin composite produce material dirt (mesh ヤ ニ), granule rupture and The increase of chip, thus there is also during fabrication and be difficult to obtain the problems such as the good molded body of outward appearance.

The polyacetal resin composite of present embodiment can significantly improve polyacetal resin and category of glass packing material Adhesivity.Therefore, even if improving the use level of category of glass packing material, the tensile break stress of molded body also improves (in Fig. 1 Curve (2)) without culminate (curve (3) in Fig. 1).(tensile break stress-65) (MPa)/category of glass packing material When the value of ratio (quality %) is more than 2.90, suppressing the embrittlement of the molded body for stress repeatedly, durability is greatly improved.

It addition, it is surprising that (tensile break stress-65) (MPa)/category of glass packing material ratio (quality %) Value is that the polyacetal resin composite of more than 2.90 expects that when the melting mixing of polyacetal resin composite dirt is (at die head periphery heap Long-pending resin, category of glass packing material) generation few, and the amount with chip that ruptures of granule also reduces.Thereby, it is possible to improve Molding cycle, and cause the raising of the outward appearance of molded body.Further, it is also possible to obtain improving the effect of the sliding of molded body.

Category of glass packing material ratio is (B) category of glass packing material of the weight relative to polyacetal resin composite Weight rate, uses the value in terms of quality %.

Category of glass packing material ratio can be obtained as follows: by polyacetal resin composite or molded body in the highest temperature Degree (more than 400 DEG C) carries out burning thus removes resinous principle, then by the weight of obtained residue divided by gathering before burning Acetal resin composition or the weight of molded body, and it is multiplied by 100 times.

In the present embodiment, in order to make the tensile break stress of molded body be more than 135MPa, the bending bullet of molded body Property modulus is more than 7500MPa and (tensile break stress-65) (MPa)/category of glass packing material ratio (quality %) is More than 2.90, can enumerate such as: use block copolymer described later as (A) polyacetal resin and to use described later comprising The film former of acid is as the film former for (B) category of glass filler.

Wherein, and with block copolymer and comprise acid film former time, (A) polyacetal resin and (B) category of glass fill material The adhesivity at the interface of material significantly improves, particularly tensile break stress and (tensile break stress-65MPa) (MPa)/category of glass The value of packing material ratio (quality %) increases.

It addition, when manufacturing polyacetal resin composite by melting mixing, (B) category of glass packing material is gathered with (A) The acetal resin mixing longer time is for increasing (tensile break stress (MPa)-65MPa)/category of glass packing material ratio (matter Amount %) value be also effective.Generally, when the melting mixing of resin combination, it is believed that preferably category of glass packing material is with relatively Short time carries out mixing, and forms contrary trend in present embodiment.Make (tensile break stress-65 (MPa))/category of glass The aspect that the value of packing material ratio (quality %) increases, specifically, can enumerate: supply by side charger when extruding mixing (B), in the case of category of glass packing material, supply from more upstream side.

The polyacetal resin composite of present embodiment is preferably following polyacetal resin composite: described polyacetal resin (B) category of glass more than (A) polyacetal resin that compositions comprises 100 mass parts and 10 mass parts and below 100 mass parts is filled out Filling material, the tensile break stress according to ISO527-1 of the molded body this polyacetal resin composite molding obtained is More than 135MPa, the modulus of elasticity in static bending according to ISO 178 of this molded body is more than 7500MPa, (tensile break stress-65) (MPa) value of/category of glass packing material ratio (quality %) is more than 2.90, additionally, to comprising the combination of this polyacetal resin When the molded body of thing carries out tension failure, from the table of (B) category of glass packing material that the plane of disruption of post-rift molded body highlights Face is averaged the composition comprising (A) polyacetal resin of below more than thickness 0.2 μm and 3.0 μm and covers.

When the molded body comprising polyacetal resin composite is carried out tension failure, cover from post-rift molded body The average thickness of the composition comprising polyacetal resin composite on the surface of (B) category of glass packing material that the plane of disruption is prominent is More than 0.2 μm and below 3.0 μm.

Being more than 0.2 μm by this average thickness, creep resistant, mechanical strength improve.It addition, can suppress chip and The bad order of the molded body obtained by suppression, therefore quality improves.Additionally, due to molding cycle shortens thus productivity ratio carries High.

It addition, be below 3.0 μm by this average thickness, it is possible under the mobility of suppression polyacetal resin composite Fall, thus suppress the bad order of molded body.

The lower limit of this average thickness is preferably 0.3 μm, more preferably 0.4 μm.

The higher limit of this average thickness is preferably 2.5 μm, more preferably 2.0 μm.

＜ (A) polyacetal resin ＞

(following below for (A) polyacetal resin that can use in the polyacetal resin composite of present embodiment Sometimes (A) composition it is denoted as) it is described in detail.

As (A) polyacetal resin that can use in the present embodiment, can enumerate: polyacetal homopolymer, polyacetals Copolymer, have cross-linked structure Copolyacetal, have block component block copolymer based on homopolymer and tool There is the block copolymer based on copolymer of block component.

(A) polyacetal resin can use independent one, it is also possible to is applied in combination two or more.

As (A) polyacetal resin, such as, can also be suitably used the different combination of molecular weight, amount of comonomers difference The combination etc. of Copolyacetal.

In the present embodiment, block copolymer is preferably comprised as (A) polyacetal resin.

As (A) polyacetal resin, specifically, can enumerate: make formaldehyde monomers or its trimer (metaformaldehyde), four gather What what the cyclic oligomer of the formaldehyde such as thing (four polyformaldehyde) carried out homopolymerization and obtained be the most only made up of oxymethylene units is poly- Acetal homopolymer；Make formaldehyde monomers or the cyclic oligomer of the formaldehyde such as its trimer (metaformaldehyde), tetramer (four polyformaldehyde) With glycol or dimerization such as oxirane, expoxy propane, epoxychloropropane, 1,3-dioxolane, 1,4-butanediol formals The Copolyacetal that the cyclic ethers such as the cyclic formals of glycol or cyclic formals carry out copolymerization and obtain.

As Copolyacetal, it is possible to use: make the monomer of formaldehyde and/or the cyclic oligomer of formaldehyde and simple function The Copolyacetal with side chain that glycidyl ether carries out copolymerization and obtains；And make the monomer of formaldehyde and/or formaldehyde The Copolyacetal with cross-linked structure that cyclic oligomer and polyfunctional glycidyl ether carry out copolymerization and obtain.

Copolyacetal can be have the different types of block different from the constitutional repeating unit of polyacetals embedding Section copolymer.

In the present embodiment, as block copolymer, preferably: at least have in following formula (1), (2) or (3) is arbitrary The acetal homopolymer of the block component shown in formula or acetal copolymer (the most sometimes both merging being designated as block copolymer).

In formula (1) and (2), R₁And R₂Represent independently of one another and select free hydrogen atom, alkyl, replacement alkyl, aryl and replacement One in the group of aryl composition, multiple R₁And R₂Each can be the same or different.

R₃Represent the one selected free alkyl, replace in the group that alkyl, aryl and substituted aryl form.

M represents the integer of 1～6, the integer of preferably 1～4.

N represents the integer of 1～10000, the integer of preferably 10～2500.

Block component shown in above-mentioned formula (1) is the residue after the alkylene oxide addition product from alcohol sloughs hydrogen atom, above-mentioned formula (2) block component shown in is the residue after the alkylene oxide addition product from carboxylic acid sloughs hydrogen atom.

The polyacetal homopolymer with the block component shown in formula (1) or (2) such as can pass through Japanese Laid-Open Patent Publication 57- Method described in No. 31918 publications is prepared.

In formula (3), R₄Represent in the group selecting free hydrogen atom, alkyl, replacement alkyl, aryl and substituted aryl composition Kind, multiple R₄Each can be the same or different.

P represents that the integer of 2～6, two p each can be the same or different.

Q and r each represents positive number, when the total of q Yu r is set to 100 moles of %, q be 2～100 moles of %, r be 0～98 Mole % ,-(CH (CH₂CH₃)CH₂)-unit and-(CH₂CH₂CH₂CH₂)-unit the most randomly exists or with the form of block Exist.

In following formula (1), (2) or (3), the block component shown in arbitrary formula can be by making at double ends or single end tool The compound the constituting block component end section with polyacetals in the polymerization process of polyacetals having the functional groups such as hydroxyl enters Row reaction, is thus inserted in polyacetal resin.

The insertion of the block component shown in formula (1), (2) or (3) in block copolymer is not particularly limited, by embedding When section copolymer is set as 100 mass %, more than for example, 0.001 mass % and below 30 mass %.

From the viewpoint of the modulus of elasticity in static bending never making molded body declines, the insertion of this block component is preferably set to Below 30 mass %, from the viewpoint of the hot strength of molded body, the insertion of this block component is preferably 0.001 mass % Above.

The lower limit of the insertion of this block component is more preferably 0.01 mass %, more preferably 0.1 mass %, more More preferably 1 mass %.

The higher limit of the insertion of this block component is more preferably 15 mass %, more preferably 10 mass %, more enters One step is preferably 8 mass %.

From the viewpoint of the modulus of elasticity in static bending never making molded body declines, the molecule of the block component in block copolymer Amount is preferably less than 10000, more preferably less than 8000, more preferably less than 5000.

The lower limit of the molecular weight of this block component is not particularly limited, and goes out from the viewpoint persistently keeping stable sliding Send out, preferably more than 100.

The compound forming the block component in block copolymer is not particularly limited, and specifically, can enumerate: C₁₈H₃₇O (CH₂CH₂O)₄₀C₁₈H₃₇、C₁₁H₂₃CO₂(CH₂CH₂O)₃₀H、C₁₈H₃₇O(CH₂CH₂O)₇₀H、C₁₈H₃₇O(CH₂CH₂O)₄₀H, double end hydroxyl Alkylation hydrogenated butadiene polymer etc..

As bonding scheme, block copolymer is preferably ABA block polymer.

ABA block polymer refers to the block copolymer with the block component shown in formula (3), specifically, refers to Make the hydrogenated butadiene polymer segment B (being denoted as B below) after polyacetals segments A (being denoted as A below) and double end hydroxyalkylation with A- The block copolymer that the order of B-A is constituted.

It is 20g-I that formula (1), formula (2) or the block component shown in formula (3) can have iodine number₂The unsaturation of/below 100g Key.As unsaturated bond, it is not particularly limited, such as carbon-to-carbon double bond can be enumerated.

The Copolyacetal with formula (1), formula (2) or the block component shown in formula (3) can enumerate such as International Publication Polyacetals block copolymer disclosed in No. 2001/09213, can be prepared by the method described in this publication.

By using ABA block polymer as block copolymer, there is surface with (B) category of glass packing material The tendency that adhesivity improves.The tensile break stress of molded body and the modulus of elasticity in static bending can be made to increase as a result of which it is, have Tendency.

(A) (A) polyacetal resin set overall is being 100 mass % by the ratio of the block copolymer in polyacetal resin Time be preferably below more than 5 mass % and 95 mass %.

The lower limit of the ratio of this block copolymer is more preferably 10 mass %, more preferably 20 mass %, more enters One step is preferably 25 mass %.

The higher limit of the ratio of this block copolymer is more preferably 90 mass %, more preferably 80 mass %, more enters One step is preferably 75 mass %.

The ratio of this block copolymer in the resin combination of present embodiment can pass through¹H-NMR、¹³C-NMR etc. enter Row measures.

＜ (B) category of glass packing material ＞

(B) the category of glass packing material that can use in the polyacetal resin composite of present embodiment is (the most sometimes It is denoted as (B) composition) it is not particularly limited, glass fibre, glass microballoon and glass flake etc. can be enumerated.

As glass fibre, can enumerate such as: chopped strand glass fibers, milled glass fiber, fibre glass roving etc.. Wherein, from the viewpoint of the mechanical strength of operability and molded body, preferably chopped strand glass fibers.

(B) category of glass packing material can use independent one, it is also possible to is applied in combination two or more.

(B) particle diameter of category of glass packing material, fibre diameter and fibre length etc. are not particularly limited, it is possible to use arbitrarily The category of glass packing material of form, (B) category of glass packing material and the contact area of (A) polyacetal resin that surface area is big increase Add, the creep resistant of molded body improves, the most preferably.

In the case of chopped strand glass fibers, more than fiber diameter for example, 7 μm and below 15 μm.

By this fiber diameter within the above range, the surface of molded body is smoothened, it is possible to suppression sliding Decline.Additionally, it is possible to increase the creep resistant of molded body, and the scraping (cutting れ) of die surface when being prevented from molding Deng.

The lower limit of this fiber diameter is preferably 8 μm, more preferably 9 μm.

The higher limit of this fiber diameter is preferably 14 μm, more preferably 12 μm.

In the present embodiment, fiber diameter can measure as follows: by molded body in the highest temperature (400 DEG C Carry out above) burning and removing resinous principle, then use the ash obtained by sem observation, and measure diameter, It is possible to easily be measured.In order to eliminate error, measure chopped strand glass fibers straight of more than at least 100 Footpath, and calculate the meansigma methods of fibre diameter.

Glass fibre can also be used in mixed way the glass fibre that two or more fibre diameters is different.

(B) category of glass packing material is preferably the category of glass packing material after making surface modification through film former process.Become Membrane is otherwise referred to as collecting agent.

As film former, specifically, can enumerate: carbamate resins, epoxy resin, have at least one acid composition Copolymer resin etc..Wherein, the film former of the copolymer resin with at least one acid composition is preferably comprised.

As have at least one acid composition copolymer resin, can enumerate such as: comprise containing carboxylic acid unsaturated ethylene thiazolinyl Monomer and except this containing the unsaturated ethylene thiazolinyl monomer in addition to carboxylic acid unsaturated ethylene thiazolinyl monomer as the copolymer of Component units；Bag Containing containing carboxylic acid anhydrides unsaturated ethylene thiazolinyl monomer and the unsaturated ethylene thiazolinyl list in addition to this is containing carboxylic acid anhydrides unsaturated ethylene thiazolinyl monomer Body is as the copolymer etc. of Component units.Wherein, more preferably use: comprise containing carboxylic acid unsaturated ethylene thiazolinyl monomer and contain carboxylic except this Unsaturated ethylene thiazolinyl monomer beyond acid unsaturated ethylene thiazolinyl monomer is as the copolymer of Component units.

Film former can be used alone one, it is also possible to is applied in combination two or more.

As containing carboxylic acid unsaturated ethylene thiazolinyl monomer, specifically, acrylic acid, methacrylic acid, fumaric acid, clothing can be enumerated Health acid, maleic acid etc., preferably acrylic acid.

The unsaturated ethylene thiazolinyl monomer containing carboxylic acid can be used alone one, it is also possible to is applied in combination two or more.

As containing carboxylic acid anhydrides unsaturated ethylene thiazolinyl monomer, specifically, the anhydride etc. in maleic acid or itaconic acid can be enumerated.

The unsaturated ethylene thiazolinyl monomer containing carboxylic acid anhydrides can be used alone one, it is also possible to is applied in combination two or more.

By utilizing the film former modifying surface to (B) category of glass packing material, it is possible to increase with (A) polyacetals tree The adhesive strength at the interface of fat, the average thickness of the layer on the surface of cover glass class packing material increases.Thus creep resistant and Tensile break stress improves.Furthermore it is possible to abrasion when suppression is slided.

Wherein, by the category of glass packing material group that the polyacetal resin comprising block component is modified with utilizing film former Closing, creep resistant and tensile break stress significantly improve.

In the present embodiment, (B) category of glass packing material can utilize coupling agent to carry out surface modification.

Coupling agent is not particularly limited, it is possible to use known coupling agent.

As coupling agent, specifically, can enumerate: organic silane compound, organo titanate compounds, organic aluminates Compound etc..

Coupling agent can be used alone one, it is also possible to is applied in combination two or more.

As organic silane compound, specifically, can enumerate: VTES, vinyl three (2-methoxy Base oxethyl) silane, γ-methacryloxypropyl methoxy silane, gamma-amino propyl trimethoxy silicane, gamma-amino Propyl-triethoxysilicane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, β-(3,4-epoxycyclohexyl) second Ethyl triethoxy silicane alkane, γ-glycidoxypropyl group methoxy silane, γ mercaptopropyitrimethoxy silane etc..

Wherein, preferably VTES, vinyl three (2-methoxy ethoxy) silane, γ-methyl-prop Alkene acryloxypropylethoxysilane methoxy silane, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane and γ-ring Oxygen propoxypropyl methoxy silane.From the viewpoint of the heat stability of economy and resin combination, more preferably vinyl Triethoxysilane, γ-glycidoxypropyl group methoxy silane and γ aminopropyltriethoxy silane.

As organo titanate compounds, specifically, can enumerate: tetraisopropyl titanate, tetra-n-butyl titanate, metatitanic acid fourth Ester dimer, metatitanic acid four stearyl ester, triethanol amine titanate, titanium acetylacetone, lactic acid titanium, octylene glycol titanate, isopropyl (N- Aminoethylamino ethyl) titanate esters etc..

As organic aluminates compound.Specifically, can enumerate: acetyl group aluminum alkoxide diiso propoxide etc..

Utilizing coupling agent to carry out the category of glass packing material that surface processes by use, the creep resistant of molded body tends to Improve further, and the heat stability of molded body tends to improving further.

＜ (C) weight average molecular weight is the polyvinyl resin ＞ of less than 500,000

In the resin combination of present embodiment, preferably comprise the polyethylene tree that (C) weight average molecular weight is less than 500,000 Fat (is denoted as (C) polyvinyl resin or (C) composition) the most sometimes.

(C) polyvinyl resin can be used alone one, it is also possible to is applied in combination two or more.

It is less than 500,000 by weight average molecular weight, it is possible to the generation of suppression chip, and in the slip of molded body Yu metal In, coefficient of friction becomes low and highly stable value.

(C) weight average molecular weight of polyvinyl resin be preferably more than 10,000 and less than 400,000, more preferably more than 1.5 ten thousand and Less than 300000, more preferably more than 20,000 and less than 200,000, the most preferably more than 30,000 and less than 150,000.

Weight average molecular weight can be measured by the following method.By the sample of polyacetal resin composite or molded body A part cuts, and impregnated in hexafluoroisopropanol (hereafter abbreviated with HFIP), is filtered off by the polyacetal resin composition dissolved.Need Illustrate, in the case of insoluble in HFIP, it is also possible to utilize hydrochloric acid decomposition etc. to remove polyacetal resin composition.

Then, undissolved residue composition is made to be dissolved in trichloro-benzenes (hereafter abbreviated with TCB) at 140 DEG C, by filtering glass Glass class packing material filters off.Use obtained filtrate, utilize gel to be impregnated with chromatography (hereafter abbreviated with GPC) and be measured. Showa Denko K. K UT-807 (1) and TOSOH Co., Ltd GMHHR-H (S) HT (2) is connected in series as The post used.Using TCB as flowing phase, test portion concentration is set as 20～30mg (polyvinyl resin)/20ml (TCB).Will Column temperature be set as 140 DEG C, flow set be 1.0ml/ minute, use differential refractometer be measured as detector.

The calculating of weight average molecular weight uses polymethyl methacrylate (hereafter abbreviated with PMMA) to carry out as standard substance Calculate.PMMA standard substance now uses in terms of number-average molecular weight in the range of about 2,000 to about 1,000,000 at least 4 samples.

(C) content of polyvinyl resin is preferably more than 0.5 mass parts and 8 relative to (A) polyacetal resin 100 mass parts Below mass parts, more than more preferably 1 mass parts and below 6 mass parts, more preferably 5 mass parts below 1.5 mass parts Below.

By making this content be more than 0.5 mass parts, sliding is good and steady in a long-term.It addition, wearability also improves.

By making this content be below 8 mass parts, it is possible to suppress the decline of mechanical strength, melted mixed at resin combination Chip during refining and the stripping in molded body (disengaging of (C) polyvinyl resin composition).

(C) content of polyvinyl resin such as can be confirmed by following method.By polyacetal resin composite Or molded body carries out burning in the highest temperature (more than 400 DEG C) and removes resinous principle.Weight according to obtained ash Amount obtains the content of (B) glass fibre.

Then, the polyacetal resin comprised in polyacetal resin composite or molded body is carried out hydrochloric acid decomposition, from residue In deduct after the match ratio of (B) glass fibre obtained before the content for (C) polyvinyl resin.It should be noted that according to Situation, it is possible to use infrared spectrum (IR) etc. confirm with or without other composition and carry out adding removing operation.

As (C) polyvinyl resin that can use in the present embodiment, specifically, can enumerate: extremely-low density gathers Ethylene, Low Density Polyethylene, high density polyethylene (HDPE), linear low density polyethylene etc..Further, it is possible to use containing 5 mass % with Under propylene, butylene, the ethene copolymer etc. of the comonomer such as octene.

Wherein, from the coefficient of friction during slip of metal from the viewpoint of, preferably Low Density Polyethylene.

Preferably containing at least a kind of fusing point of (C) polyvinyl resin that can use in the present embodiment (hereafter abbreviated with Tm) it is the polyvinyl resin of less than 115 DEG C.More preferably Tm is less than 110 DEG C.

Being less than 115 DEG C by Tm, with the slip of metal, coefficient of friction becomes low and highly stable.It addition, logical When crossing melting mixing manufacture polyacetal resin composite, give play to the effect of the moment of torsion that extruder can be greatly reduced.Thus, energy The increase of enough outputs realizing in the past being difficult in the polyacetal resin composite with category of glass packing material.

In the present embodiment, Tm uses: the sample using polyacetal resin composite or the sample 4 cut from molded body ～6mg (preferably being laminated by compacting etc.), utilize differential scanning calorimetry (DSC) gained when the intensification of 10 DEG C/min The peak value of the heat absorption arrived.

＜ stabilizer ＞

The molded body of the polyacetal resin composite of present embodiment do not damage in the range of the purpose of the present invention permissible Comprise the various stabilizers generally used in polyacetal resin composite.

Stabilizer is not particularly limited, and specifically, can enumerate: antioxidant；Formaldehyde, the agent for capturing etc. of formic acid.

Stabilizer can be used alone one, it is also possible to is applied in combination two or more.

As antioxidant, from the viewpoint of the heat stability improving molded body, preferably hindered phenol anti-oxidants.Make For hindered phenol anti-oxidants, it is not particularly limited, known hindered phenol anti-oxidants can be suitably used.

The addition of antioxidant is preferably more than 0.1 mass parts and 2 matter relative to (A) polyacetal resin 100 mass parts Below amount part.

As formaldehyde, the agent for capturing of formic acid, specifically, can enumerate: tripolycyanamide, polyamide-based resin etc. comprise formaldehyde Reactive nitrogen compound and polymer thereof；Alkali metal or the hydroxide of alkaline-earth metal, inorganic acid salt, carboxylate etc..

More specifically, calcium hydroxide, calcium carbonate, calcium phosphate, calcium silicates, Calcium pyroborate, fatty acid calcium salt (tristearin can be enumerated Acid calcium, calcium myristate etc.) etc..These fatty acids can be optionally substituted by a hydroxyl group.

The addition of agent for capturing is preferably following scope: relative to (A) polyacetal resin 100 mass parts, as formaldehyde, first The polymer comprising formaldehyde reactive nitrogen of the agent for capturing of acid is below more than 0.1 mass parts and 3 mass parts, the fat of alkaline-earth metal Fat hydrochlorate is below more than 0.1 mass parts and 1 mass parts.

＜ other composition ＞

The molded body of the polyacetal resin of present embodiment can also contain in the range of the purpose of the present invention not damaging Packing material (Talcum, silicon ash known in the past using in polyacetal resin composite, in addition to category of glass filler Stone, Muscovitum, calcium carbonate etc.), conductivity-imparting agent (white carbon black, graphite, CNT etc.), coloring agent (titanium oxide, zinc oxide, oxygen Change ferrum, aluminium oxide, organic dyestuff etc.), slip imparting agent (various ester type compounds, the slaine etc. of organic acid), ultraviolet inhale Receive the various stabilizers such as agent, light stabilizer, lubriation material.

About the addition of other composition, for the packing material in addition to glass fibre, conductivity-imparting agent, coloring agent For, it is preferably below 30 mass % when polyacetal resin being set as 100 mass %, for slip imparting agent, ultraviolet For absorbent, light stabilizer, lubriation material, it is preferably below 5 mass % relative to polyacetal resin 100 mass %.

Other composition can be used alone one, it is also possible to is applied in combination two or more.

Manufacture method ＞ of ＜ molded body

The molded body of present embodiment can utilize known method to manufacture.Specifically, can be single by utilizing Screw rod or multiscrew mixing extruder, roller, Banbury etc. are as described below to be mixed material composition and melting mixing And be shaped and manufacture.Wherein it is possible to be preferably used be equipped with decompressor side charger equipment twin screw squeeze Go out machine.

As material composition being mixed and the method for melting mixing, it is not particularly limited, it is possible to use this area skill Method known to art personnel.Specifically, can enumerate: (A) composition and (B) composition are advanced with super blender, rotary drum Mixer, V-arrangement batch mixer etc. mix, and the method utilizing the disposable melting mixing of double screw extruder；(A) composition is supplied Carry out melting mixing to double screw extruder main feed oral area, and add the method etc. of (B) composition from the midway of extruder. Any one in these methods can be utilized, in order to improve the mechanical properties of the molded body of present embodiment, preferably: (A) become Divide supply to double screw extruder main feed oral area to carry out melting mixing, and add the side of (B) composition from the midway of extruder Method.Optimal conditions change according to the size of extruder, the most preferably in the range of those skilled in the art can regulate Suitably regulate.More preferably: for the screw design of extruder, also enter in the range of those skilled in the art can regulate The various regulations of row.

When coordinating (C) composition, it is also possible to be added from the midway of extruder, but preferably carry out from main feed oral area Supply.By using such manufacture method, it was surprisingly found that can also obtain being greatly reduced the effect of the moment of torsion of extruder Really.Thereby, it is possible to greatly improve productivity ratio.

It is not particularly limited for obtaining the forming method of the molded body in present embodiment, it is possible to use known molding Method.Specifically, it is possible to use extrusion molding, injection moulding, vacuum forming, blow molding, injection compression molding, be decorated Type, dissimilar materials molding, air-auxiliary injection forming, foam injection molding, low pressure molding, ultra-thin-wall injection moulding (ultrahigh speed Injection moulding), any one in the forming method such as composite molding (molding on insert moulding, inserts) is shaped in mould.

The amount ＞ of (C) polyvinyl resin in the top layer of ＜ molded body

For the molded body of present embodiment, preferably: (C) weight average molecular weight in the top layer of molded body be 500,000 with Under polyvinyl resin amount more than by the degree of depth on the top layer away from molded body more than the table in the face after the layer cutting of 1,000 μm The amount of the polyvinyl resin that (C) weight average molecular weight is less than 500,000 in Ceng.

(C) amount of polyvinyl resin is according to the unit relatively of the carbon C using X-ray photoelectron spectroscopy (XPS) to measure Element concentration (atom %) calculates.As determinator, can enumerate such as: Thermo Fisher Scientific Co., Ltd. system ESCALAB250 etc..

As excitaton source when measuring, use monoAlK α etc..It addition, in order to get rid of the attachment being attached to molded body surface The impact of pollutant component, for molded body surface, carries out ultrasound wave with detergent (aqueous solution of such as VALTRON DP97031) Washing, washs with pure water, is dried with baking oven etc..Photoelectron exit angle is set as 0 ° (vertical with molded body), catches Range set is wide range scanning (Survey Scan) 0～1100eV, narrow spectrum scanning (Narrow Scan) carbon C is the region of 1s. It addition, logical can (Pass Energy) be set as wide range scanning (Survey scan) be 100eV, narrow spectrum scanning (Narrow Scan) it is 20eV.In XPS measures, being the carbon being derived from polyacetal resin in conjunction with energy 286～288eV, 284～286eV for being derived from The carbon of the alkene such as polyethylene, therefore at the carbon that can only use the composition being derived from polyethylene in the case of detached peaks.Can not divide In the case of peak, it is possible to use the peak area of the scope of 284～288eV.

Use the concentration of carbon C in the top layer of molded body₁, by the central part of molded body, (degree of depth of molded body is more than 1000 μm Layer portion) the concentration of carbon C on top layer in face after cutting₂Time, [C₁]/[C₂] ＞ 1 relational expression set up time, it may be said that molded body Top layer in deep more than by the top layer away from molded body of the amount of the polyvinyl resin that (C) weight average molecular weight is less than 500,000 Degree is more than the existence of the polyvinyl resin that (C) weight average molecular weight is less than 500,000 in the top layer in the face after the layer cutting of 1000 μm Amount.

It should be noted that in the present embodiment, C is measured₂Position be set as that the degree of depth of molded body is more than 1000 μm Layer portion, in the molded body obtained in the polyacetal resin composite molding by present embodiment, as long as away from its top layer The degree of depth is more than the layer portion of 100 μm, no matter then position, the amount of (C) polyvinyl resin and rate of charge are roughly the same value.

It is preferably 1.01≤[C₁]/[C₂]≤1.20, more preferably 1.02≤[C₁]/[C₂]≤1.18, more preferably 1.05≤[C₁]/[C₂]≤1.15。

It should be noted that there is the block copolymer of the block component shown in above-mentioned formula (3) as polyacetals in use In the case of resin, the concentration of carbon of polyacetal resin increases self.But, the source in the layer portion more than 1000 μm on top layer and the degree of depth Not there are differences from the concentration of carbon of polyacetal resin, thus when above formula is set up, it may be said that in top layer, there is substantial amounts of (C) gather Vinyl.

Gather by being more than existence more (C) in the layer portion of 1000 μm than the degree of depth at molded body in the top layer of molded body Vinyl, the sliding at initial stage of particularly sliding improves.It addition, cunning can just be significantly improved by coordinating a small amount of polyethylene The effect of dynamic property, therefore, it is possible to the decline of the mechanical strengths such as the suppression modulus of elasticity in static bending.Further, it is also possible to obtain in resin combination Suppression chip such wonderful effect during the melting mixing of thing.

It should be noted that in the case of the thickness molded body less than 2000 μm, it is possible to use the degree of depth side of molded body To central part concentration of carbon replace the degree of depth more than 1000 μm layer portion in concentration of carbon.

In order to make the top layer of molded body be more than (C) polyvinyl resin in the layer portion of 1,000 μm more than the degree of depth of molded body How to exist, can be by the weight average molecular weight of (C) polyvinyl resin joined together be set as that less than 500,000 realize.This Outward, by the Tm of (C) polyvinyl resin is set as less than 115 DEG C, so that (C) the polyethylene tree in the top layer of molded body The amount of fat is more than the amount of (C) polyvinyl resin in the layer portion of 1,000 μm more than the degree of depth of molded body.

[purposes]

The polyacetal resin composite of present embodiment can serve as requiring the molding of durability, mechanical strength and wearability The raw material of body.

The molded body of present embodiment can be suitable as automotive part, especially can be suitable for and other parts Playing as gear, the parts of the effect of pulley of contact.

In addition, additionally it is possible to be applied to the known purposes of the purposes as polyacetal resin.Specifically, permissible It is applied to: with cam, slide block, lever, arm, clutch, felt clutch, idler gear, roller, cylinder, key core, keycap, baffle plate, volume The mechanism part that axle, rotary shaft, joint, axle, bearing, pulley, guide rail etc. are representative；The resin component of molding, inserts on inserts The resin component of molding, chassis, pallet, side plate, the door lock as automobile component, door handle, window regulator, window regulator The door associated components that spool, loudspeaker grid, glass supporter etc. are representative；Peace with seat belt slip ring, button etc. as representative Full band circumferential component；The parts such as cubicle switch parts, Switch, fixture class；With fuel tank, fuel pump module, valve class, oil tank flange Deng the fuel associated components for representative, with printer and photocopier the office automatic equipment parts as representative；DV, The video equipment parts such as digital camera；CD, DVD, Blu-ray Disc, the driver of other CD；With navigation system and movement PC is the music of representative, video or information equipment；The communication equipment parts as representative with mobile phone and facsimile machine；Electrically If spare unit；Electronic equipment parts etc..It addition, as other articles for use, can enumerate: the nib of writing implement, make core come in and go out Mechanism part；Washstand, discharge outlet, drain cock switching mechanism parts；The cotton rope retainer of dress material, actuator, button；Spread The nozzle of water, spread water tube hose jointing；As balustrade portion and the building product of the support member of flooring material；Toy, Securing member, chain, conveyer, bracelet, sporting goods, automatic vending machine (switch portion latching device, commodity discharging gear release mechanism parts), Furniture, musical instrument, residential equipment machine part etc..

Embodiment

Hereinafter, by embodiment and comparative example, present embodiment is specifically described, as long as present embodiment does not surpasses Go out its purport, be then not limited to these embodiments and comparative example.

The polyacetal resin composite used in embodiment and comparative example and the manufacturing condition of molded body and assessment item As described below.

(1) extrusion

Use the spiro rod length L ratio (L/D)=48 (barrel number 12) relative to screw diameter D, at the 6th barrel and the 8th material Cylinder has side charger, and possesses co-rotating twin screw extruder (the toshiba machine strain of vaccum exhaust outlet at the 11st barrel Formula commercial firm TEM-48SS extruder).1st barrel is carried out water-cooled, the 2nd～5 barrels are set as 210 DEG C, by the 6th～12 material Cylinder is set as 180 DEG C.

Screw rod for extrusion uses following design.In the position of the 1st～4 barrels, configuration thread screw (is abridged below For FS), it is configured with successively in the position of the 5th barrel and there is the kneading disk (hereafter abbreviated with RKD) 2 pieces of conveying capacity, without conveying The kneading disk (hereafter abbreviated with NKD) 2 pieces of ability and there is the kneading disk (hereafter abbreviated with LKD) to reciprocal conveying capacity 1 piece.Configure FS in the position of the 6th～the 8th barrel, configure each one piece of RKD and NKD in the position of the 9th barrel successively, the 10th～ The position configuration FS of the 11st barrel.

(preparation method 1)

By the side charger supply category of glass packing material of the 6th barrel, setting screw speed 150rpm, total extrusion capacity sets For 70kg/ hour, extrude.

(preparation method 2)

By the side charger supply category of glass packing material of the 8th barrel, setting screw speed 150rpm, total extrusion capacity sets For 70kg/ hour, extrude.

(2) extrusion rate

Moment of torsion during above-mentioned extrusion is used for the evaluation of extrusion rate.

Judging that the numerical value of moment of torsion is the least, the most easily extrude, being more improved the leeway of the velocity of discharge, extrusion rate is the highest.

(3) material dirt amount

The material dirt produced near die head when above-mentioned extrusion is reclaimed, and measures the material dirt amount of time per unit.

When material dirt amount is few, productivity ratio, quality are good.

(4) scrap rate

After above-mentioned extrusion, in the line material cutter in the gap of 7/1000, put into the strands of 80 DEG C and carry out pelletize.Do not lead to Cross particle-size distributor.

Obtained granule 1kg ± 0.1kg is added in three times the sieve of 14 mesh, through the weight of mesh divided by being used for sieving Particle weight, thus obtain the amount of chip.Being worth the least then chip the fewest, quality is the best.

(5) making of the molded body of compact tensile test film shape

Using injection (mo(u)lding) machine (EC-75NII, Toshiba Machinery Co., Ltd.'s system), barrel temperatures set is set as 205 DEG C, Injecting condition in 35 seconds injection time, 15 seconds cool times is shaped, and resulting in and draws according to the small-sized of ISO294-2 Stretch the molded body of test film shape.Mold temperature is set to 90 DEG C.One-tenth by the compact tensile test film shape according to ISO294-2 Type body is in each mensuration of following (6)～(8), (10), (12) and (14).

As the creep test test film of the mensuration for following (9) creep fracture time, obtain according to JIS The molded body of the compact tensile test film shape of K7139-5A.Mold temperature set is 90 DEG C.

(6) tensile break stress

Use the molded body obtained in above-mentioned (5), within 5mm/ minute, carry out stretching examination according to ISO527-1 with draw speed Test, determine tensile break stress.

(7) modulus of elasticity in static bending

Use the molded body obtained in above-mentioned (5), be curved test according to ISO 178, determine elasticity of flexure mould Amount.

(8) average thickness of the composition on the surface of cover glass class packing material

Use the molded body obtained in above-mentioned (5), within 50mm/ minute, utilize tension test to make molded body break with draw speed Split.The plane of disruption at molded body is deposited with platinum, thus makes observation test film.Use observation test film, utilize scanning electron Microscope (SEM) is observed, and thus measures.Carry out observing under conditions of multiple is 5000 times.

As look-out station, it is adjusted making it possible to observe the plane of disruption central part of observation test film.From fracture Arbitrary 50 are selected among the glass fibre that face is prominent.For all glass fibre, all confirm resinous principle and cover equably Cover the surface that cross section is circular glass fibre.Then, the diameter of the glass fibre covered by resinous principle is measured. It addition, according to by advance test film being burned 3 hours and the glass fibre that remove resinous principle and obtain straight at 450 DEG C The difference in footpath (meansigma methodss of 100), has obtained the thickness of the resinous principle being attached to surface.Carry out addition for 50 and ask flat All, as the average thickness of composition on surface of cover glass class packing material.

(9) creep fracture time

Use the molded body as creep test test film obtained in above-mentioned (5), use creep testing machine (east Ocean essence mechanism Zuo Suo Co., Ltd. system), the load applying 25MPa under 80 DEG C of environment carries out creep test, measures to being fractured into Time only.Carry out three times to measure, be averaged value as creep fracture time.When numerical value is big, creep resistant is excellent.

(10) to SUS304 ball wear depths with to the SUS304 ball coefficient of kinetic friction

Use the molded body obtained in above-mentioned (5), employ ball-dish-type reciprocal dynamic friction abrasion tester (AFT- 15MS type, Precision Co., Ltd of Japan system).23 DEG C, in the environment of humidity 50%, load 19.6N, the linear velocity 30mm/ second, Reciprocal distance 20mm, the condition of reciprocal time 5000 times have carried out sliding test.Ball material use SUS304 ball be (diameter 5mm's Ball).After using confocal microscope (OPTELICS (registered trade mark) H1200, Lasertec Co., Ltd. system) to sliding test The wear extent (wearing depth) of sample is measured.To putting down of the numerical value that the employing of the SUS304 ball wear degree of depth is measured with n=5 Average.When numerical value is low, excellent in abrasion resistance.

It addition, in sliding test, the coefficient of kinetic friction in the moment carrying out 1000 slips is moved as to SUS304 ball Coefficient of friction (initial sliding), carries out the coefficient of kinetic friction the moving SUS304 ball as molded body in the moment slided 5000 times Coefficient of friction.When numerical value is low, excellent in sliding property.

(11) to the SS400 flat board coefficient of kinetic friction

Use injection (mo(u)lding) machine (Ti30G2, Toyo Jukikai Metal Corp.'s system), be 90 DEG C by mold temperature set, machine Cylinder design temperature is set as 200 DEG C, is shaped, thus makes under injection speed 40%, the injecting condition of 3 seconds injection time Front end is the spherical resin cotter of 5mm.

Use ball-dish-type reciprocal dynamic friction abrasion tester (AFT-15MS type, Precision Co., Ltd of Japan system).23 DEG C, in the environment of humidity 50%, in load 39.2N, linear velocity 30mm/ second, reciprocal distance 20mm, reciprocal time 10000 times Under the conditions of, use SS400 metal plate to make as disk material, the spherical resin cotter using above-mentioned front end to be diameter 5mm For ball material, evaluated.Using carry out 10000 times the coefficient of kinetic friction in moment that slides as molded body to SS400 flat board The coefficient of kinetic friction.When numerical value is low, excellent in sliding property.

(12) to the own material coefficient of kinetic friction

Use ball-dish-type reciprocal dynamic friction abrasion tester (AFT-15MS type, Precision Co., Ltd of Japan system).23 DEG C, in the environment of humidity 50%, at load 19.6N, linear velocity 30mm/ second, reciprocal distance 20mm, the bar of reciprocal time 5000 times Under part, using the molded body obtained in above-mentioned (5) as disk material, using the front end obtained in above-mentioned (11) is diameter The spherical resin of 5mm is made and sold as ball material, is evaluated.The coefficient of kinetic friction work in the moment slided will be carried out 5000 times For molded body to the own material coefficient of kinetic friction.When numerical value is low, excellent in sliding property.

(13) molding cycle

Use injection (mo(u)lding) machine (α 50i-A, FANUC Co., Ltd's system), be set as barrel zone temperature 190 DEG C, mold temperature 80 DEG C, injection pressure 120MPa, carry out the molding of the spur gear (single-chamber) of modulus 0.8, the number of teeth 50, facewidth 5mm.Now, injection Time with 5 seconds as lower limit, cool time with 15 seconds as lower limit, the time needed for the metering of resin more than in the case of 15 seconds, Improving screw speed during metering, regulation makes Dose times shorten.Improving screw speed shortly, the time needed for metering is the biggest In the case of 15 seconds, Dose times will be set as+3 seconds cool time.Carry out 20 minutes continuously shaped under this condition.

The length of cool time and the number of every 20 minutes continuously shaped gears to each sample now are surveyed Amount, as the metewand of molding productivity ratio.Now, if metering requires time for (according to circumstances also increasing cool time), then one Time required for secondary injection increases, and therefore molding cycle increases, and productivity ratio declines.

(14) the existence ratio (surface polyethylene ratio) of the polyvinyl resin in the top layer of molded body

Use X-ray photoelectron spectroscopy (XPS) ESCALAB250 of Thermo Fisher Scientific company, Use monoALK α (15kV × 10mA) as excitaton source.It is square that analysis is dimensioned so as to 1mm.In order to remove the top layer of molded body Attachment, use 1.5% aqueous solution of commercially available precision equipment detergent (VALTRON DP97031), at the bar of 50 DEG C Carry out 3 minutes ultrasonic washings under part, thus remove the Organic substance on surface, then with high performance liquid chromatography distilled water in room temperature Under the conditions of carry out 15 minutes ultrasonic Treatment and implement washing.Then, will washing after sample carry out in drying oven 80 DEG C, For measuring after 1 hour dried.In this mensuration, photoelectron exit angle is set as 0 ° (vertical with molded body), capture area Territory be set as wide range scanning (Survey Scan) be 0～1100eV, narrow spectrum scanning (Narrow Scan) carbon C be the region of 1s. It addition, for logical energy (Pass Energy), wide range scanning (Survey scan) be 100eV, narrow spectrum scanning (Narrow Scan) it is enforcement under conditions of 20eV.C concentration now is set to the peak area ratio of the scope of 284eV to 288eV.According to area Ratio calculates relative elemental concentrations, rounds up, and the concentration of 1 more than atom % calculates with 2 position effective digitals, is less than The concentration of 1 atom % calculates with 1 position effective digital.As measuring sample, use the molded body obtained in above-mentioned (5). Concentration of carbon in the top layer of this molded body is set as [C₁].Then, the thickness direction of ultramicrotome excision forming body is utilized Central authorities, by the concentration of carbon [C near the same central part measured thickness direction₂] be measured.

(15) cantilever bending vibrating fatigue

Using injection (mo(u)lding) machine (EC-75NII, Toshiba Machinery Co., Ltd.'s system), barrel temperatures set is 200 DEG C, mould Temperature is set as 80 DEG C, under conditions of 10 seconds cool times, molds the flat of length 12cm × width 8cm × thickness 0.3cm Plate is as test film.With the direction parallel with the filling direction of resin during molding for measuring the mode in direction, carry out cutting and add Work becomes the shape according to ASTM D671TYPE1, thus has obtained test film.Utilize Toyo Seiki Co., Ltd. repetitive vibrations Fatigue machine, by the method according to ASTM D671-B method under conditions of number of repetition 1800 beats/min, temperature 23 DEG C This test film is measured, is 10 by the number of repetition in bend test⁶Stress or the test film of fracture is there is time secondary Maximum deflection exceed before fracture ± stress (kgf/m of 8mm²) as the value of cantilever bending vibrating fatigue.Value is by from obtaining Minimum 5 reach about 10⁴～about 10⁷The curve of secondary point reads 10⁶Secondary value and obtain.Be worth the biggest, then durability is the most excellent Different.

(16) SFD (helical flow distance (Spiral Flow Distance))

Use injection (mo(u)lding) machine (FANUC Co., Ltd ROBOSHOT α-50iA), by barrel temperatures set be 200 DEG C, Mold temperature set is 80 DEG C, uses SFD mould thick for 2mm to be evaluated the SFD of each composition of injection pressure 80MPa.SFD Value the longest, then mobility is the most excellent.

Hereinafter the material composition of the polyacetal resin composite used in embodiment and comparative example and molded body is carried out Explanation.

(A1) ProductName: Tenac (registered trade mark)-C 4520 (Asahi Chemical Corp's system), melt flow rate (MFR) (MFR)=9.0g/10 minute, number-average molecular weight Mn=about 70,000

(A2) ProductName: Tenac (registered trade mark)-C 7520 (Asahi Chemical Corp's system), melt flow rate (MFR) (MFR)=45.0g/10 minute, number-average molecular weight Mn=2.5 ten thousand

(A3) polyacetals block copolymer is prepared as follows.By continuous for the dual-axis paddle of the chuck with the thermal medium that can circulate Polymerization machine regulates to 80 DEG C.The metaformaldehyde of 40 mols/hr, the work of 2 mols/hr is continuously fed in above-mentioned polymerization machine For the 1,3-dioxolane of cyclic formals, be 5 × 10 relative to metaformaldehyde 1 mole^-5Mole amount conduct polymerization The boron trifluoride di-n-butyl etherate being dissolved in hexamethylene of catalyst, it is 1 × 10 relative to metaformaldehyde 1 mole^-3Mole Double terminal hydroxyl hydrogenated butadiene polymers (number-average molecular weight Mn=2,330) shown in following formula as chain-transferring agent (5) of amount, And be polymerized.

Then, above-mentioned polymerization machine the polymer discharged is put in triethylamine 1% aqueous solution, makes polymerization catalyst complete After inactivation, by polymer filtration, washing, thus obtain thick polyacetals block copolymer.

Relative to obtained thick polyacetals block copolymer 100 mass parts, add and (be recorded in day containing quaternary ammonium compound No. 3087912 publication of this patent) aqueous solution 1 mass parts, uniformly mix.The addition of quaternary ammonium compound is converted into nitrogen Amount is 20 mass ppm.It is supplied to the double-screw type extruder to band air vent, relative to melted bunching in an extruder Aldehyde block copolymer 100 mass parts, adds the water of 0.5 mass parts.Delay in extruder design temperature 200 DEG C, extruder Under conditions of 7 minutes time, the decomposition of the unstable end section carrying out polyacetals block copolymer removes.

Polyacetals block copolymer after unstable end section is decomposed adds three second two as antioxidant Double [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester] 0.3 mass parts of alcohol, utilizes the extruder of band air vent Carry out removing volatile ingredient under conditions of vacuum 20 torr, be extruded into strands from extruder die head, and carry out pelletize.

Using thus obtained polyacetals block copolymer as (A3) polyacetals block copolymer.This block copolymer is ABA block polymer, melt flow rate (MFR) is 15g/10 minute (ISO-1133 condition D).Calculated by melt flow rate (MFR) Number-average molecular weight Mn be about 50,000.

(B) category of glass packing material uses following category of glass packing material.

(B1) utilize the film former that the manufacture example 1 of No. 4060831 publications of Japanese Patent No. is recorded (containing acrylic acid and propylene Acid methyl ester copolymer) etc. process after glass fibre.

(B2) utilize the film former that the embodiment 1 of Japanese Unexamined Patent Publication 2012-136385 publication is recorded (containing comprising acrylic acid Copolymer) etc. process after glass fibre.

(B3) film former (not containing acid) utilizing the sample No.1 of Japanese Unexamined Patent Publication 2009-7179 publication to record is located Glass fibre after reason.

(C) polyvinyl resin uses following polyvinyl resin.

(C1) Asahi Chemical Corp Suntec (registered trade mark) LD L1850A

Weight average molecular weight 13.2 ten thousand, Tm=107 DEG C, density 918kg/m³

(C2) Asahi Chemical Corp's system, Suntec (registered trade mark) HD J240

Weight average molecular weight 7.3 ten thousand, Tm=127 DEG C, density 966kg/m³

(C3) Asahi Chemical Corp Sunfine (registered trade mark) BM840

Weight average molecular weight 32.4 ten thousand, Tm=126 DEG C, density 931kg/m³

(C4) Asahi Chemical Corp Sunfine (registered trade mark) UH901

Molecular weight (viscosimetry) 3,300,000, Tm=136 DEG C, density 940kg/m³

The mensuration of weight average molecular weight uses (C) polyvinyl resin in 140 DEG C of solution being dissolved in TCB and obtain, following institute State and be measured by GPC.By Showa Denko K. K UT-807 (1) and TOSOH Co., Ltd GMHHR-H (S) HT (2) are connected in series as the post used.Using TCB as flowing phase, sample solution concentration is set as 20～30mg ((C) poly-second Olefine resin)/20ml (TCB).Column temperature is set as 140 DEG C, and flow set is 1.0ml/ minute, uses differential refractometer as inspection Survey device, be determined.

The calculating of weight average molecular weight uses PMMA to calculate as standard substance.

It should be noted that the molecular weight of (C4) is high, comprise the composition insoluble in trichloro-benzenes, it is impossible to carry out utilizing GPC's Molecular weight determination, therefore measures molecular weight by the viscosimetry according to JIS K7367-3.

[embodiment 1～13, comparative example 1～6]

Carry out under conditions of described in table 1 or table 2 in the way of each composition each reaches the ratio of table 1 or table 2 record Extrude manufacture resin combination.Obtained resin combination is used to be shaped under these conditions and manufactured molding Body.The evaluation result of each physical property will be shown in table 1, table 2 and table 5.

[table 1]

[table 2]

In embodiment 1～13, the average thickness of resin on the surface covering (B) category of glass packing material be 0.2 μm～ The scope of 3.0 μm.Thus, creep resistant, wearability, sliding and molding productivity ratio are good.

Wherein, as embodiment 1～8 and embodiment 13, make using the polyacetal resin (A3) with block component Utilize the category of glass packing material (B1 or B2) of the film former modification comprising acid as (B) glass for (A) polyacetal resin and use In the case of glass class packing material, the average thickness of composition on the surface covering (B) category of glass packing material be up to 0.8 μm with On.Thus, not only creep resistant and sliding improve further, and when can reduce manufacture material dirt, the amount of chip.

On the other hand, in comparative example 1～5, the average thickness of the composition covering the surface of (B) category of glass packing material is low To 0.2 μm.

Wherein, as comparative example 1～3, do not using the polyacetal resin (A3) with block component as (A) bunching Urea formaldehyde and category of glass packing material (B1 or B2) conduct (B) category of glass not using utilization to comprise sour film former modified are filled In the case of material, on the surface of (B) category of glass filler entirely without observing the coating of resin.In this case, no Only creep resistant, wearability, sliding and molding productivity ratio declines, and material dirt, the amount of chip when manufacturing also increases.

Embodiment 9 and comparative example 4 are carried out contrast understand, mixing by use after importing (B) category of glass packing material The preparation method 1 of time length, the average thickness of the resin covering the surface of (B) category of glass packing material tends to increasing.

Embodiment 1 and comparative example 6 are carried out contrast understand, the comparative example 6 that use level at (B) category of glass packing material is few In, even if the average thickness of resin covering the surface of (B) category of glass packing material is enough 1.2 μm, also can not get improving resistance to The effect of the degree of creep properties.

[embodiment 14～26, comparative example 7～9]

Carry out under conditions of table 3 or table 4 are recorded in the way of the ratio that each composition each reaches described in table 3 or table 4 Extrude and manufactured resin combination.Obtained resin combination is used to be shaped under these conditions and manufactured molding Body.The evaluation result of each physical property is shown in table 3～table 5.

[table 3]

[table 4]

In embodiment 14～26, the average thickness of resin on the surface covering (B) category of glass packing material be 0.2 μm～ The scope of 3.0 μm, creep resistant, wearability, sliding and molding productivity ratio are good.Further, containing these of (C) polyethylene In embodiment, wearability, sliding improve further.

Contrast according to embodiment 14,15 and the contrast of embodiment 17,22,23,24, using weight average molecular weight In the case of being the polyethylene (C1, C2 or C3) of less than 500,000, polyethylene easily concentrates on molded body surface, it is possible to carry further High sliding, wearability.

On the other hand, in comparative example 7～9, owing to not using the polyacetal resin (A3) with block component as (A) Polyacetal resin and do not use the category of glass packing material (B1 or B2) utilizing the film former comprising acid modified as (B) category of glass Packing material, therefore on the surface of (B) category of glass filler entirely without observing the coating of resin.In this case, see Material dirt when observing the decline of creep resistant and manufacture, the increase of the amount of chip.

[table 5]

The application is based on Japanese patent application filed in 28 days March in 2014 (Japanese Patent Application 2014-070201), in it Hold and be incorporated by reference in this specification.

Industrial applicability

The polyacetal resin composite of the present invention and molded body in the various fields of applicable use polyacetal resin, especially The field of the automobile mechanism parts of requirement durability and sliding has industrial applicability.

Claims (12)

1. a polyacetal resin composite, described polyacetal resin composite comprise 100 mass parts (A) polyacetal resin and (B) category of glass packing material more than 10 mass parts and below 100 mass parts, wherein,

When the molded body this polyacetal resin composite molding obtained is carried out tension failure, from post-rift molded body The surface of prominent (B) the category of glass packing material of the plane of disruption be averaged below more than thickness 0.2 μm and 3.0 μm comprise (A) The composition of polyacetal resin covers.

2. a polyacetal resin composite, described polyacetal resin composite comprise 100 mass parts (A) polyacetal resin and (B) category of glass packing material more than 10 mass parts and below 100 mass parts, wherein,

The tensile break stress according to ISO527-1 of the molded body this polyacetal resin composite molding obtained is More than 135MPa,

The modulus of elasticity in static bending according to ISO 178 of this molded body is more than 7500MPa, and

(tensile break stress-65) (MPa)/category of glass packing material ratio (quality %) is more than 2.90.

3. polyacetal resin composite as claimed in claim 2, wherein, to by described polyacetal resin composite molding When the molded body obtained carries out tension failure, from prominent (B) the category of glass packing material of the plane of disruption of post-rift molded body Surface is averaged the composition comprising (A) polyacetal resin of below more than thickness 0.2 μm and 3.0 μm and covers.

4. the polyacetal resin composite as according to any one of claims 1 to 3, wherein, relative to described (A) polyacetals tree Fat 100 mass parts, described polyacetal resin composite also comprises (C) Weight-average molecular of below more than 0.5 mass parts and 8 mass parts Amount is the polyvinyl resin of less than 500,000.

5. polyacetal resin composite as claimed in claim 4, wherein, described (C) weight average molecular weight be less than 500,000 poly- The fusing point of vinyl is less than 115 DEG C.

6. the polyacetal resin composite as according to any one of Claims 1 to 5, wherein, described polyacetal resin composite Comprise at least one acid material as the function of the modifying surface having described (B) category of glass packing material.

7. polyacetal resin composite as claimed in claim 6, wherein, described acid is carboxylic acid.

8. the polyacetal resin composite as according to any one of claim 1～7, wherein, described (A) polyacetal resin comprises Block component.

9. polyacetal resin composite as claimed in claim 8, wherein, described block component is hydrogenated butadiene polymer composition.

10. a molded body, it is by obtaining the polyacetal resin composite molding according to any one of claim 1～9 Arrive.

11. molded bodys as claimed in claim 10, wherein, it is less than 500,000 that described molded body comprises (C) weight average molecular weight Polyvinyl resin, the amount of the polyvinyl resin that (C) weight average molecular weight is less than 500,000 in the top layer of molded body is more than will The degree of depth on the top layer away from molded body more than 1,000 μm layer cutting after face top layer in (C) weight average molecular weight be 500,000 with Under the amount of polyvinyl resin.

The manufacture method of the polyacetal resin composite according to any one of 12. 1 kinds of claim 1～9, comprising:

Utilization comprises at least one acid and has the material pair of function of modifying surface to (B) category of glass packing material (B) operation of the modifying surface of category of glass packing material；With

The operation that category of glass packing material and (A) polyacetal resin through described modification is mixed.